Treatment bath



Patented Feb. 22,1943

ikalien Handels- A.-G., Zurich, Switzerland, a corporationof SwitzerlandN Drawing. Application May 4, 1939, Serial No. 211,112. In Germany May5, 1938 9 Claims; (cl, 8-54) This invention relates to a method forpreventing the dissipation or loss of strength of agents which are bothanion active and capillary active in baths during their" use forthetre'atment of various types, of nitrogenous materials. It alsorelates to the treatment baths themselves containing anion active andcapillary active agents which maintain their original efficiencythroughout the period of treatment.

Itis a known fact that the efiectveness' of acid baths and neutral bathsas ordinarily employed in. the treatment of nitrogen-containingmaterials such as, textiles, furs, fibrous materials and the like, whichinclude agents which are both anion activeand capillary active,decreases during the course of the treatment period unless the operatorcontinually adds further quantities of such agents to the baths. Thisfact is easily verified by a consideration of the readily observedcharacteristic decrease in the foaming properties examination of thetreated materials has shown that a considerable portion of these anionand capillary active substances is absorbed by the materials treated,thereby decreasing the concentration of these substances in the baths toa point where their effectiveness is practically lost. This absorptionresults in needless interruption in the continuity of the process and ina dissipation of expensive raw materials and frequently-without .20 ofthese baths in the course of treatment. Closer a compensatoryimprovements-in the ultimate product.

It isa principal object of this invention. to provide a method whichstabilizes anion active and capillary active agents in treatment bathsfor nitrogen-containing materials. Another object of the invention is toprovide treatment baths for nitrogen-containing materials theeifectiveness of which does not diminish during. use with respect ateelectrolytically in aqueous solutions, to such baths before or duringthe treatment of the nitrogenous materials. No loss of the anion activeI "substances occurs through absorption by the v nitrogenous materialsbeing treated, and hence the eiiectiveness of the treatment baths ismaintainedthroughout the treatment process. This invention, therefore,makes it possible to overcome a disadvantage inherent in the priorcompositions and processes.

The anion active and capillary active substances suitable for use inthis invention, broadly considered, include all those capillary activesubstances which ionize negatively in aqueous solutions. In general,these anion active and capillary active compounds are characterized byhavphatic aromatic or aliphatic hydro-aromatic hydrocarbon radicals; Rrepresents a divalent acyclic or cyclic hydrocarbon radical which mayalso contain hetero-atoms or hetero-atomic radicals, such as, oxygen,sulfur, nitrogen, halogen, hydroxyl, ether radicals, and the like; Xrepresents a hetero-atom or a hetero-atomic group, such as, forinstance, oxygen, sulfur, nitrogen, sulfonyl, carbonyl ester, acid amideand like radicals, or x may be omitted; and G represents an acidradical, preferably an inorganic salt-forming acid radical capable ofbeing later neutralized with a base to form water-soluble salts,examples of suitable acids being,'for instance, the sulfuric acid esterradical, the sulfonic acid radical, the thinsulfuric acid ester radical,the phosphoric acid ester radical, the pyro-phosphoric acid esterradical, the boric acid esterradical, and where the treatments are inneutral baths the carboxylic radical. Suitable salts are those formed,for instance, with an alkali metal, ammonia, or .amine radical. Suchsubstances include, for instance, water-soluble salts of highermolecular fatty alcohol sulfonates and of -higher molecular sulfonicacids, and also water-soluble salts of the sulfonates of glycerine andpoly-glycerine esters of ethers. Other such substances are water-solublesalts of taurine, taurine substituted on the nitrogen atom by highermolecular fatty acid groups. N-methyl taurlne, and other amino alklysulfonic acids, as well as the water-soluble salts of isothionic acidand other hydroxy alkyl sulfonic acids esterified with higher molecularfatty acids.

Specific capillary active and anion active compounds suitable for use inthe treatment baths v monostearic acid ester, omega-butyl ether of decylsulfuric acid ester, phosphoric acid esters of the pentanediolmonoacetates, omega-hexyl thioethers of octyl thiosulfuric acid esters,N- butyl amino dodecyl sulfuric acid ester, sulfuric acid ester ofbeta-hydroxm gamma-(sec. octyl cresoxy) propanes, sec. octyl phenoxyethane useful in the practice of the invention are, for

sulfuric acid ester, dodecoxy acetic acid, N-

oleoyl methyl beta-amino ethane sulfonic acid, stearoyl beta-oxyethanesulfonic acid, N-cetyi sulfone sulfanilic acid, omega-cyclo hexyl etherof decane sulfonic acid, sec. octyl phenyl benzyl ether 4-sulfonic acid,mixtures of isomeric 2-is0 alkyl cresoxy benzoic acid sulfonic acids (5)(alkyl groups with 5-11 carbon atoms), l-sec. octyl phenoxy benzene2,4-disulfonic acid, l-sec. hexyl phenoxy 2-(acetyl amino) benzene4-sulionic acid, the sulfuric,reaction product of sec.

octyl ortho-cresyl benzylether, sulfuric reaction 7 product of thecresoxy acetic acid dodecyl amide and similar compounds, and thewater-soluble salts of these compounds, as with alkali metals, ammonia,organic bases and the like.

Baths containing these anion active and capillary active substances maybe used in known manner for the treatment of nitrogen-containingmaterials, such as textiles, furs, leathers, skins, hairs, especiallyliving hair, feathers, and the like. For instance, wool, artificialwool, natural silk, nitrogen-containing cellulosic substances, and thelike are treated'in various forms, such as in the form of flakes,threads, ribbons, strands as well as in the form of spun and wovenfabrics. Animal hides, leathers, skins, hairs, feathers, furs and theirdressed products are likewise treated in such baths. These anion activeand capillary active substances are used therein for various purposesincluding the generation of foam, or for emulsifying, dispersing,wetting, peptizing, stabilizing, equivalizing, dividing, dis-' solving,or like purposes in processes involving washing, cleaning, dyeing,coloring, and the like. These anion active and capillary active agentsmay amount to from 0.01% to of the bath guthusually constitute from0.05% to 3% of such at s.

The capillary active agents which are stable against electrolyticdissociation and which are suitable as stabilizing agents in thepractice of the instant invention include such compounds. for instance,as polyethers,-;2polyether alcohols and polyalcohols which in part arederived from higher molecular organic compounds, and higher molecularamino oxides.

Polyethers of higher molecular organic compounds of satisfactorystructure are already known per se. Such compounds may be obtained bythe action of alkylene oxides on higher molecular organic acyclic andcyclic compounds having at least one hydrogen atom in the moleculecapable of reacting with the alkylene oxide whereby as many moles ofalkylene oxide, as a rule at least 4 moles, are added as are required tomake the condensation product water soluble. Compounds containinghydrogen atoms capable of reaction are, for instance, compounds withhydroxyl, mercapto, sulfine, amino, substituted amino, carboxyl and likeradicals. Suitable alkylene oxides include such oxides as ethyleneoxide, propylene oxide and the like. Similar products can .be producedby forming addition products with several moles of glycols, forinstance, ethylene glycol, propylene glycol and the like.

. octyl cresol, di-hydroxy-di-phenyl drogenation product with about 10or more moles of ethylene oxide per hydroxyl group.

Polyether alcohols of higher molecular organic compounds suitable foraddition to 'the treatment baths of this invention are also known per seand include the water-soluble condensation products of polyglycerine,and the like, with higher molecular organic compounds, such as fattyacids; mineral acid esters of higher molecular alcohols and the like.Similar products are likewise obtained by the reaction of glycide withhigher molecular hydrocarbons having at least one hydrogen atom capableof reaction with glycide, such as, for instance, higher molecularhydroxyl-, mercapto-, and amino-compounds and the like. Polyetheralcohols of this nature are, for instance, octyl polyglycerine ether, dodecyl polyglycerine ether, palmitic acid polyglycerine ester, oleic acidpolyglycerine ester, the condensation product obtained from one mole ofstearic acid amide and 10 moles of glycide and the like.

Polyether compounds of the type described as Polyalcohol condensationproducts derived from higher molecular organic compounds and used in thetreatment baths of this invention are known per se and include thecondensation products of higher molecular acyclic and cyclic hydroxyl,carboxyl, amino and like compounds with polyalcohols; such as, forinstance, the

o lauric acid and ricinoleic acid esters of the sorbites, dulcites ormannites, the higher molecular alkyl or alkyl aryl ethers of thesepolyalcohols; the hydrogenated condensation products of higher molecularamines with glucose, mannose, fructose and the like, such as, forinstance, octyl glucamine, dodecyl glucamine, and the like.

Certain higher molecular water-soluble amino oxides have utility in thetreatment baths of the invention because they likewise do not dissociateelectrolytically in aqueous solutions. They include, for instance,oxides of dodecyl dimethyl amine, dodecyl di-ethyl amine, dodecylpyridine, lauryl di-ethyl ethylene di-amine and the like.

The surface active compounds mentioned heretofore as being stableagainst electrolytic dissociation in aqueous solutions may be appliedupon the scope of the invention.

Example 1 Dyed woolens arewashed at 50 C. in awarm washing bath having amaterial to bath ratio of 1:50 an containing acetic acid to' preventbleeding out of the dye and also containing per I liter, as a foaming,wetting and cleaning agent, 2.5 grams of the sodium salt of a commercialsulfuric acid .ester mixture derived from cocoanut oil fatty alcoholsand as a capillary active agent stable against hydrolyticdissociation-1.5 grams of the condensation product obtained from onemole of a commercial mixture of octadecyl and hexadecyl alcohol withabout 15 moles of ethylene oxide. Analytical tests and an observation offoaming characteristics vof the bath proves that the sodium. salt of themixture of the cocoanut oil fatty alcohol sulfuric acid esters remainedin the bath and was not taken up by the fibers.

If the capillary active agent stable against hydrolytic dissociation isnot added as the washing process progresses the bath loses its foam ingcapacity and thereby part of its 'eilectiveness because the sulfuricacid ester salt is ab sorbed by the wool. 1

Example 2 A dy bath for woolen yarns, is prepared in a dye vatcontaining 4% of a slightly equalizing acid wool dye, such as, forinstance, acid-fast Examples As in Example 2, woolen yarns are dyed in abath containing 12% Glaubers salt, 4% acetic acid of 30% strength, 6%Supramine brown (a material to bath ratio of 1:40), and 2 grams of thesodium salt of the N-oleyl methyl beta-amino ethane sulfonic acid perliter of dye liquor as a wetting and equalizing agent. The Schultznumber of Supramine brown is not known but the dyestufi is described inSchultz, Farbstofltabellen,

Erganzungsband I (1934) page 135. In order to prevent the wetting andequalizing agent from being almost completely absorbed by the goods inthe first batch treatment, there is added 1.2 grams of the condensationproduct of a mixture of diand tri-iso-butyl cresol and about 12 moles ofethylene oxide for every liter of the dye liquor It should be understoodthat the present invention is not limited to the specific materials,

blue B having the Schultz No. 825, 12% crystallized Glaubers salt, 3%sulfuric acid (66. 1%.), calculated on the material to be dyed and as awetting and equalizing agent 2 grams of the sodium salt of laurylsulfuric acid ester per liter of dye liquor. One grain of aperhydroger'iated condensation productobtained from a mixture ofisomeric sec. alkyl cresols (obtained from condensation of cresol witholefines from benzine synthesis) and about 16 to 1'! moles ethyleneoxide is added to the dye bath before the-dyeing operation.- Thematerial to be" dyed is introduced at 50 C. (material to bath ratio oi1:40)

- andfthe temperature is raised to boiling, where- "upon the dyeingiscomplete. The sodium salt of the sulfuric acid ester of lauryl alcoholremains almost completely intact in the bath upon j completion of thedyeing process. It is not necessary to add a portion of this agent whenintroguctilng new materials into the freshened dye a a In such baths asthose just described, the absence of the perhydrogenated ethylene oxidealkyl cresol condensation product or similar products results not onlyin the absorption of the dye but almost all of the sodium salt 01.sulfuric acid ester of lauryl alcohol is absorbed by the wool fiberlikewise. when replenishing the dye substance in the mother liquor undersuch circumstances, it is always necessary to add also the sodium saltof the sulfuric acid ester of lauryl alcohol.

- said amount ranging from about 5% to-about compositions and processesherein disclosed but that it extends to all equivalents which oneskilled in the art would consider within the general purport of theinstant disclosure as limited only by the tenor of the specification andthe requirements of the appended claims. I

I claim:

1. In the treatment of nitrogen-containing fibrous materials withacidreacting baths containing anion active saponaceous substancescomposed of a lipophilic group of at least 6 carbon atoms and ahydrophilic inorganic salt-forming acid radical neutralized with a baseof the group consisting of alkalies', ammonia and inorganic baseswherein the nitrogen-containing fibrous materials absorb substantialquantities of said saponaceous substances, the step which comprisesapplying said baths to said materials in the presence of an organicwater-soluble surface active agent which is electro-neutral in aqueoussolutions in an amount ranging from about 5% to about 50% of thequantity of said anion'active -active' substance which iselectro-neutral in aqueous solutions in an amount which substantiallycompletely prevents the absorption of said sulfonated alcohol by saidfibrous materials, said amount ranging from about 5% to about 50% of thequantity of said sulfonated alcohol.

3. The process of stabilizing the effectiveness of organic treatingagents which are both anion active and capillary active and are composedof a lipophilic group of at least 6 carbon atoms and a hydrophilicinorganic salt-forming acid radical in acidic treatment baths fornitrogen-containing fibrous materials which absorb said anion activetreating agents comprising adding to such baths organic water-solublecapillary active substances which are stable against electrolyticdissociation in aqueous solutions in an amount which substantiallycompletely prevents the absorption of said anion active agents by saidfibrous materials,

50% of the anion active substances.

4. In the treatment of a nitrogen-containing fibrous material with anacidic bath containing a water-soluble salt of an organic treating agentwhich is both anionactive and capillary active and is composed of alipophilic group of at least presence of a capillary active agent whichis stable against electrolytic dissociation in aqueous solutions in anamount which substantially completely prevents the absorption of saidanion active agent by said fibrous material, said amountranging fromabout 5% to about 50% of the quantity of the anion active agent.

5. In the treatment of nitrogen-containing fibrous materials in acid dyebaths which require the presence of an organic treating agent havingboth anion active and capillary active properties and being composed ofa lipophilic group of at least 6 carbon atoms and a hydrophilicinorganic salt-forming acid radical wherein the fibrous materials absorbsubstantial quantities of the anion active agent, the step whichcomprises applying said anion active agent to the nitrogencontainingfibrous materials in, the presence of other organic water-solublecapillary active agents which are stable against electrolyticdissociation in aqueous solutions in an amount which substantiallycompletely prevents the absorption of said anion active agent by saidfibrous materials, said amount being about 50% of the quantity of saidanion active substance.

6. An acid dye bath for treating nitrogencontaining fibrous materialscomprising a dye component, an organic treating agent which is bothanion active and capillary active and is composed of a lipophilic groupof at least 6 carbon atoms and a hydrophilic inorganic salt-forming acidradical and an organic water-soluble capillary active agent which isstable against hydrolytic dissociation in aqueous solutions in an amountwhich substantially completely prevents the absorption of said anionactive agent by said fibrous materials, said amount being about 50% ofthe quantity of said anion active agent.

7. An acidic treatment liquor for nitrogencontaining fibrous materialscontaining as wetting, dispersing and cleaning agents the combination ofan organic substance which is both anion active and capillary activewith an organic water-soluble capillary active agent which is stableagainst ionic dissociation in aqueous solutions in an amount whichsubstantially completely prevents the absorption of said anion activeagent by said fibrous materials, said amount ranging from about 5% toabout of the quantity of said anion active substance.

8. In the process of treating wool in an acid bath with an organictreating agent composed of an aliphatic lipophilic group of at least 6carbon atoms and a hydrophilic sulfonate group wherein the wool absorbssubstantial quantities of said treating agent, the step which comprisessubstantially completely preventing the wool from absorbing saidtreating agent by incorporating in the acid treating bath from 5% to 50%of a capillary active substance which does not dissociateelectrolytically in aqueous solution, the quantity of said capillaryactive substance being based upon the quantity of said treating agent.

9. In the 'process of treating wool in an acid dye bath with an organictreating agent composed of an aliphatic lipophilic group of at least 6carbon atoms and a hydrophilic sulfonate group wherein the wool absorbssubstantial quantities of said treating agent, the step which comprisessubstantially completely preventing the wool from absorbing saidtreating agent by incorporating in the acid dye bath from 5% to 50% of acompound having the formula wherein R is a lipophilic hydrocarbon groupand n is at least 4, the quantity of said compound being based upon thequantity of said treating agent.

ERNST GC'rI'rE.

